CN114621673A - 一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法 - Google Patents
一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法 Download PDFInfo
- Publication number
- CN114621673A CN114621673A CN202210281477.6A CN202210281477A CN114621673A CN 114621673 A CN114621673 A CN 114621673A CN 202210281477 A CN202210281477 A CN 202210281477A CN 114621673 A CN114621673 A CN 114621673A
- Authority
- CN
- China
- Prior art keywords
- protective coating
- parts
- polyether
- modified polyurethane
- polysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 polysiloxane Polymers 0.000 title claims abstract description 79
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 51
- 239000011253 protective coating Substances 0.000 title claims abstract description 49
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 43
- 229920000570 polyether Polymers 0.000 title claims abstract description 43
- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 22
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 230000008034 disappearance Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- YAXKTBLXMTYWDQ-UHFFFAOYSA-N 1,2,3-butanetriol Chemical compound CC(O)C(O)CO YAXKTBLXMTYWDQ-UHFFFAOYSA-N 0.000 claims description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004386 Erythritol Substances 0.000 claims description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- IZSANPWSFUSNMY-UHFFFAOYSA-N cyclohexane-1,2,3-triol Chemical compound OC1CCCC(O)C1O IZSANPWSFUSNMY-UHFFFAOYSA-N 0.000 claims description 2
- FSDSKERRNURGGO-UHFFFAOYSA-N cyclohexane-1,3,5-triol Chemical compound OC1CC(O)CC(O)C1 FSDSKERRNURGGO-UHFFFAOYSA-N 0.000 claims description 2
- RHINSRUDDXGHLV-UHFFFAOYSA-N decane-1,2,10-triol Chemical compound OCCCCCCCCC(O)CO RHINSRUDDXGHLV-UHFFFAOYSA-N 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 2
- 229940009714 erythritol Drugs 0.000 claims description 2
- 235000019414 erythritol Nutrition 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- CTRCJSPDRXFNNN-UHFFFAOYSA-N heptane-1,2,7-triol Chemical compound OCCCCCC(O)CO CTRCJSPDRXFNNN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CUUVVDHSUIKLPH-UHFFFAOYSA-N nonane-1,2,9-triol Chemical compound OCCCCCCCC(O)CO CUUVVDHSUIKLPH-UHFFFAOYSA-N 0.000 claims description 2
- GKCGJDQACNSNBB-UHFFFAOYSA-N octane-1,2,8-triol Chemical compound OCCCCCCC(O)CO GKCGJDQACNSNBB-UHFFFAOYSA-N 0.000 claims description 2
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 229920001748 polybutylene Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011527 polyurethane coating Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 20
- 229920003023 plastic Polymers 0.000 description 11
- 239000004033 plastic Substances 0.000 description 11
- 230000004580 weight loss Effects 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CARUROOZSQMSHD-UHFFFAOYSA-N 3-butyl-4-[2-(2-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound CCCCC1=CC(O)=CC=C1C(C)(C)C1=CC=C(O)C=C1CCCC CARUROOZSQMSHD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
- C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08J2475/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本发明提供了一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法,由如下重量份数的组分组成:羟烷基封端的聚硅氧烷5~500份,羟基封端的聚醚5~500份,多元醇类化合物0.1~10份,二异氰酸酯0.5~80份,丙烯酸酯封端剂0.5~40份,光引发剂1~20份,催化剂0.5~10份,阻聚剂0.5~10份。本发明制得的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,具有聚硅氧烷链段、聚醚链段、氨基甲酸酯基团和丙烯酸酯基团,并具有高度支化的结构特点,具有可调节的力学性能、优异的加工性能、优异的耐热耐水耐溶剂性能、固化过程快速易实施,符合低碳环保的理念,在空气氛围下快速紫外光固化的超支化保护涂料,进一步拓宽了传统有机硅改性聚氨酯涂料的应用领域。
Description
技术领域
本发明涉及保护涂料技术领域,尤其涉及一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法。
背景技术
塑料是现代社会不可缺少的材料,其应用范围非常广泛,其中一些涉及特定应用的高科技产品,例如柔性电子产品的外壳,由于其表面硬度较差,许多塑料的应用领域受到限制。且在塑料成型加工过程中,由于热塑或热固工艺的高温条件,树脂内部微量空气及挥发性杂质的散逸导致塑料表面出现微量气孔,从而导致光泽度下降。因此,为了解决这类问题,开发低成本、高性能、固化工艺简便的塑料保护涂料成为保护涂料领域的热门话题。
目前市面上常见的塑料保护涂料为聚氨酯丙烯酸酯型涂料,其具有耐磨性优异、固化速度快、易于加工等优势,被广泛应用于各类塑料件的表面保护中。然而,由于聚氨酯丙烯酸酯本身存在储存稳定性差、预聚物粘度高、热稳定性差、耐酸、碱、乙醇和水等化学性差等问题,需要对其进行改性以便扩展其应用。
超支化聚合物一类高度支化的三维大分子,超支化聚合物支化点多,分子链不易缠结,黏度不随着分子量的增加而改变,且具有丰富的末端官能团,易对其进行修饰改性,有利于合成多样的功能性材料。合成具有超支化结构的聚氨酯丙烯酸酯,有望解决预聚物粘度过大的问题,极大地改善了涂料的加工性能。
有机硅因其独特而优越的性能,如表面自由能低、玻璃化转变温度低、低温弹性大,以及良好的热、化学和生物稳定性,良好的水和耐候性等,可以有效地改善聚氨酯丙烯酸酯的各类性能缺陷。但是,由于有机硅本身的机械强度极低,容易导致涂料呈现软而弱的性能特点,因此在引入有机硅的基础上,引入部分聚醚链段,以在保证耐水、溶剂性质的基础上,提高涂料的韧性。
发明内容
本发明的目的一在于公开一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,具有聚硅氧烷链段、聚醚链段、氨基甲酸酯基团和丙烯酸酯基团,并具有高度支化的结构特点,具有可调节的力学性能、优异的加工性能、优异的耐热耐水耐溶剂性能、固化过程快速易实施,符合低碳环保的理念,在空气氛围下快速紫外光固化的超支化保护涂料,进一步拓宽了传统有机硅改性聚氨酯涂料的应用领域。
为实现上述目的,本发明提供了一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,由如下重量份数的组分组成:羟烷基封端的聚硅氧烷5~500份,羟基封端的聚醚5~500份,多元醇类化合物0.1~10份,二异氰酸酯0.5~80份,丙烯酸酯封端剂0.5~40份,光引发剂1~20份,催化剂0.5~10份,阻聚剂0.5~10份。
在一些实施方式中,所述羟烷基封端的聚硅氧烷分子结构如下式所示:
其中,R1—CH3~C18H37中的一种或几种;
R2—C2H4~C8H16中的一种或几种;
Mn=600~12000g/mol。
在一些实施方式中,所述羟基封端的聚醚为聚乙二醇、聚丙二醇、聚丁二醇、聚戊二醇、聚己二醇中的一种或几种,其中Mn=400~20000g/mol。
在一些实施方式中,所述多元醇类化合物为甘油、季戊四醇、1,2,3-丁三醇、1,2,4-丁三醇、1,2,5-戊三醇、1,2,6-己三醇、1,2,7-庚三醇、1,2,8-辛三醇、1,2,9-壬三醇、1,2,10-癸三醇、1,2,3-环己三醇、1,3,5-环己三醇、赤藓糖醇、双季戊四醇、三季戊四醇中的一种或几种,所述多元醇类化合物为支化中心。
在一些实施方式中,所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯中的一种或几种。
在一些实施方式中,所述丙烯酸酯封端剂为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、季戊四醇三丙烯酸酯、双季戊四醇五丙烯酸酯中的一种或几种。
在一些实施方式中,所述光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮,2,4,6-三甲基苯甲酰基-二苯基氧化膦,2,4,6-三甲基二苯甲酮和4-甲基二苯甲酮的混合物,安息香双甲醚,二苯甲酮,1-羟基-环己基苯甲酮,α,α′-乙氧基苯乙酮,α-胺烷基苯酮中的一种或几种。
在一些实施方式中,所述催化剂为有机锡化合物、有机铋化合物、钛酸酯类化合物、α硅烷偶联剂、路易斯酸类、路易斯碱类化合物中的一种或几种。
在一些实施方式中,所述阻聚剂为对苯二酚、对叔丁基邻苯二酚、2,6-二叔丁基对甲基苯酚、4,4'-二经基联苯、双酚A、对苯醌、吩噻嗪中的一种或几种。
本发明的目的二在于公开一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料的制备方法,所制得的保护涂料具有聚硅氧烷链段、聚醚链段、氨基甲酸酯基团和丙烯酸酯基团,并具有高度支化的结构特点,具有可调节的力学性能、优异的加工性能、优异的耐热耐水耐溶剂性能、固化过程快速易实施,符合低碳环保的理念,在空气氛围下快速紫外光固化的超支化保护涂料,进一步拓宽了传统有机硅改性聚氨酯涂料的应用领域。
为实现上述目的,本发明提供了一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料的制备方法,包括如下步骤:将多元醇类化合物烘干,烘干后溶于足量二甲苯中,加入二异氰酸酯,搅拌均匀后,加入催化剂,升温反应;再投入羟烷基封端的聚硅氧烷和羟基封端的聚醚,反应;最后向体系内投入阻聚剂,搅拌均匀后投入丙烯酸酯封端剂,反应;反应全程保持通入氮气并冷凝回流,反应结束以NCO特征峰消失为准;将制得的保护涂料与光引发剂混合均匀后,涂布于PET或聚酰亚胺基材上,在空气氛围下进行紫外光照,紫外光波长310-460nm,固化时间5-35s,得到紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂层。
与现有技术相比,本发明的有益效果是:本发明制得的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,具有聚硅氧烷链段、聚醚链段、氨基甲酸酯基团和丙烯酸酯基团,并具有高度支化的结构特点,具有可调节的力学性能、优异的加工性能、优异的耐热耐水耐溶剂性能、固化过程快速易实施,符合低碳环保的理念,在空气氛围下快速紫外光固化的超支化保护涂料,进一步拓宽了传统有机硅改性聚氨酯涂料的应用领域。
具体实施方式
下面结合各实施方式对本发明进行详细说明,但应当说明的是,这些实施方式并非对本发明的限制,本领域普通技术人员根据这些实施方式所作的功能、方法、或者结构上的等效变换或替代,均属于本发明的保护范围之内。
实施例一:
本实施例公开了一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法,具体内容如下:
10g双季戊四醇在103℃烘箱中烘干24h,烘干后溶于足量二甲苯中,加入52.5g异氟尔酮二异氰酸酯,搅拌均匀后,加入5g二月桂酸二丁基锡,温度升至75℃并恒温,反应1小时。
之后向体系内投入101g羟烷基双封端聚硅氧烷(Mn=858g/mol)、56g聚丙二醇(Mn=474g/mol),反应温度80℃,反应3小时。
最后向体系内投入8g对苯醌,搅拌均匀后投入70.5g季戊四醇三丙烯酸酯,反应温度70℃,反应4小时。
反应全程保持通入氮气并冷凝回流,反应结束以NCO特征峰消失为准。
将制得的聚硅氧烷/聚醚改性聚氨酯丙烯酸酯100g与5g2-羟基-2-甲基-1-苯基-1-丙酮混合均匀后,涂布于电晕的PET薄膜上,在波长范围为310-460nm紫外灯下光照20s后,得到塑料保护涂层,测试结果如下:
表1:力学性能测试
拉伸模量(MPa) | 拉伸强度(MPa) | 断裂伸长率(%) | |
数值 | 556±12 | 20.7±0.2 | 6.8±0.8 |
表2:耐热性、铅笔硬度及附着力测试
耐热性(5%失重/℃) | 铅笔硬度 | 附着力 | |
数值 | 213 | 5H | 5B |
实施例二:
本实施例公开了一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法,具体内容如下:
10g季戊四醇在103℃烘箱中烘干24h,烘干后溶于足量二甲苯中,加入49.5g六亚甲基二异氰酸酯,搅拌均匀后,加入7g二月桂酸二丁基锡,温度升至70℃并恒温,反应0.7小时。
之后向体系内投入257.5g羟烷基双封端聚硅氧烷(Mn=2342g/mol)、243g聚丙二醇(Mn=1366g/mol),反应温度75℃,反应1.5小时。
最后向体系内投入10g对苯醌,搅拌均匀后投入87.5g季戊四醇三丙烯酸酯,反应温度70℃,反应4小时。
反应全程保持通入氮气并冷凝回流,反应结束以NCO特征峰消失为准。
将制得的聚硅氧烷/聚醚改性聚氨酯丙烯酸酯100g与5g2-羟基-2-甲基-1-苯基-1-丙酮混合均匀后,涂布于电晕的PET薄膜上,在波长范围为310-460nm紫外灯下光照20s后,得到塑料保护涂层,测试结果如下:
表3:力学性能测试
拉伸模量(MPa) | 拉伸强度(MPa) | 断裂伸长率(%) | |
数值 | 183±11 | 45.2±3.4 | 56.5±5.8 |
表4:耐热性、铅笔硬度及附着力测试
耐热性(5%失重/℃) | 铅笔硬度 | 附着力 | |
数值 | 287 | 2H | 4B |
实施例三:
本实施例公开了一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法,具体内容如下:
10g双季戊四醇在103℃烘箱中烘干24h,烘干后溶于足量二甲苯中,加入52.5g异氟尔酮二异氰酸酯,搅拌均匀后,加入5g二月桂酸二丁基锡,温度升至75℃并恒温,反应1小时。
之后向体系内投入152g羟烷基双封端聚硅氧烷(Mn=858g/mol)、80g聚丙二醇(Mn=1366g/mol),反应温度80℃,反应3小时。
最后向体系内投入8g对苯醌,搅拌均匀后投入70.5g季戊四醇三丙烯酸酯,反应温度70℃,反应4小时。
反应全程保持通入氮气并冷凝回流,反应结束以NCO特征峰消失为准。
将制得的聚硅氧烷/聚醚改性聚氨酯丙烯酸酯100g与5g2-羟基-2-甲基-1-苯基-1-丙酮混合均匀后,涂布于电晕的PET薄膜上,在波长范围为310-460nm紫外灯下光照20s后,得到塑料保护涂层,测试结果如下:
表5:力学性能测试
拉伸模量(MPa) | 拉伸强度(MPa) | 断裂伸长率(%) | |
数值 | 448±21 | 17.7±0.1 | 37±1.1 |
表6:耐热性、铅笔硬度及附着力测试
耐热性(5%失重/℃) | 铅笔硬度 | 附着力 | |
数值 | 255 | 3H | 5B |
实施例四:
本实施例公开了一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法,具体内容如下:
10g双季戊四醇在103℃烘箱中烘干24h,烘干后溶于足量二甲苯中,加入52.5g异氟尔酮二异氰酸酯,搅拌均匀后,加入5g二月桂酸二丁基锡,温度升至75℃并恒温,反应1小时。
之后向体系内投入50g羟烷基双封端聚硅氧烷(Mn=858g/mol)、242g聚丙二醇(Mn=1366g/mol),反应温度80℃,反应3小时。
最后向体系内投入8g对苯醌,搅拌均匀后投入70.5g季戊四醇三丙烯酸酯,反应温度70℃,反应4小时。
反应全程保持通入氮气并冷凝回流,反应结束以NCO特征峰消失为准。
将制得的聚硅氧烷/聚醚改性聚氨酯丙烯酸酯100g与5g2-羟基-2-甲基-1-苯基-1-丙酮混合均匀后,涂布于电晕的PET薄膜上,在波长范围为310-460nm紫外灯下光照20s后,得到塑料保护涂层,测试结果如下:
表7:力学性能测试
拉伸模量(MPa) | 拉伸强度(MPa) | 断裂伸长率(%) | |
数值 | 431±12 | 35.7±0.5 | 79±10.8 |
表8:耐热性、铅笔硬度及附着力测试
耐热性(5%失重/℃) | 铅笔硬度 | 附着力 | |
数值 | 201 | 3H | 4B |
实施例五:
本实施例公开了一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法,具体内容如下:
10g双季戊四醇在103℃烘箱中烘干24h,烘干后溶于足量二甲苯中,加入59g4,4’-二苯基甲烷二异氰酸酯,搅拌均匀后,加入5g二月桂酸二丁基锡,温度升至75℃并恒温,反应1小时。
之后向体系内投入101g羟烷基双封端聚硅氧烷(Mn=858g/mol)、56g聚丙二醇(Mn=474g/mol),反应温度80℃,反应3小时。
最后向体系内投入8g对苯醌,搅拌均匀后投入35g季戊四醇三丙烯酸酯,15.5g丙烯酸羟丙酯,反应温度70℃,反应4小时。
反应全程保持通入氮气并冷凝回流,反应结束以NCO特征峰消失为准。
将制得的聚硅氧烷/聚醚改性聚氨酯丙烯酸酯100g与5g2-羟基-2-甲基-1-苯基-1-丙酮混合均匀后,涂布于电晕的PET薄膜上,在波长范围为310-460nm紫外灯下光照20s后,得到塑料保护涂层,测试结果如下:
表9:力学性能测试
拉伸模量(MPa) | 拉伸强度(MPa) | 断裂伸长率(%) | |
数值 | 607±5.7 | 24.3±0.1 | 7.7±0.8 |
表10:耐热性、铅笔硬度及附着力测试
耐热性(5%失重/℃) | 铅笔硬度 | 附着力 | |
数值 | 289 | 6H | 5B |
实施例六:
本实施例公开了一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法,具体内容如下:
10g甘油在103℃烘箱中烘干24h,烘干后溶于足量二甲苯中,加入81.5g4,4’-二苯基甲烷二异氰酸酯,搅拌均匀后,加入5g二月桂酸二丁基锡,温度升至75℃并恒温,反应1小时。
之后向体系内投入140g羟烷基双封端聚硅氧烷(Mn=858g/mol)、222.5g聚丙二醇(Mn=1366g/mol),反应温度80℃,反应3小时。
最后向体系内投入8g对苯醌,搅拌均匀后投入90.5g季戊四醇三丙烯酸酯,11.5g双季戊四醇五丙烯酸酯,反应温度70℃,反应4小时。
反应全程保持通入氮气并冷凝回流,反应结束以NCO特征峰消失为准。
将制得的聚硅氧烷/聚醚改性聚氨酯丙烯酸酯100g与5g2-羟基-2-甲基-1-苯基-1-丙酮混合均匀后,涂布于电晕的PET薄膜上,在波长范围为310-460nm紫外灯下光照20s后,得到塑料保护涂层,测试结果如下:
表11:力学性能测试
拉伸模量(MPa) | 拉伸强度(MPa) | 断裂伸长率(%) | |
数值 | 297±35 | 19±0.8 | 63±5.1 |
表12:耐热性、铅笔硬度及附着力测试
耐热性(5%失重/℃) | 铅笔硬度 | 附着力 | |
数值 | 195 | 4H | 4B |
对本发明获得的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料分子结构进行举例如下(以双季戊四醇为支化中心、季戊四醇三丙烯酸酯为封端剂):
其中,R1—CH3~C12H25中的一种或几种;
R2—H~C2H5中的一种或几种。
对比例:市售产品(有机硅改性聚氨酯涂料)
表13:力学性能测试
拉伸模量(MPa) | 拉伸强度(MPa) | 断裂伸长率(%) | |
对比例1 | 509±44 | 14±0.2 | 27±10.3 |
对比例2 | 159±36 | 7.6±0.4 | 8.8±4.2 |
表14:耐热性、铅笔硬度及附着力测试
耐热性(5%失重/℃) | 铅笔硬度 | 附着力 | |
对比例1 | 164 | 4H | 2B |
对比例2 | 284 | HB | 3B |
比较表1-14可知:本发明制得的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,由于具有聚硅氧烷链段、聚醚链段、氨基甲酸酯基团和丙烯酸酯基团,并具有高度支化的结构特点,因而具有可调节的力学性能、优异的加工性能、优异的耐热耐水耐溶剂性能、固化过程快速易实施,符合低碳环保的理念,在空气氛围下快速紫外光固化的超支化保护涂料,进一步拓宽了传统有机硅改性聚氨酯涂料的应用领域。
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施方式的具体说明,它们并非用以限制本发明的保护范围,凡未脱离本发明技艺精神所作的等效实施方式或变更均应包含在本发明的保护范围之内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (10)
1.一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,其特征在于,由如下重量份数的组分组成:羟烷基封端的聚硅氧烷5~500份,羟基封端的聚醚5~500份,多元醇类化合物0.1~10份,二异氰酸酯0.5~80份,丙烯酸酯封端剂0.5~40份,光引发剂1~20份,催化剂0.5~10份,阻聚剂0.5~10份。
3.根据权利要求1所述的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,其特征在于,所述羟基封端的聚醚为聚乙二醇、聚丙二醇、聚丁二醇、聚戊二醇、聚己二醇中的一种或几种,其中Mn=400~20000g/mol。
4.根据权利要求1所述的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,其特征在于,所述多元醇类化合物为甘油、季戊四醇、1,2,3-丁三醇、1,2,4-丁三醇、1,2,5-戊三醇、1,2,6-己三醇、1,2,7-庚三醇、1,2,8-辛三醇、1,2,9-壬三醇、1,2,10-癸三醇、1,2,3-环己三醇、1,3,5-环己三醇、赤藓糖醇、双季戊四醇、三季戊四醇中的一种或几种,所述多元醇类化合物为支化中心。
5.根据权利要求1所述的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,其特征在于,所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯中的一种或几种。
6.根据权利要求1所述的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,其特征在于,所述丙烯酸酯封端剂为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、季戊四醇三丙烯酸酯、双季戊四醇五丙烯酸酯中的一种或几种。
7.根据权利要求1所述的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,其特征在于,所述光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮,2,4,6-三甲基苯甲酰基-二苯基氧化膦,2,4,6-三甲基二苯甲酮和4-甲基二苯甲酮的混合物,安息香双甲醚,二苯甲酮,1-羟基-环己基苯甲酮,α,α′-乙氧基苯乙酮,α-胺烷基苯酮中的一种或几种。
8.根据权利要求1所述的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,其特征在于,所述催化剂为有机锡化合物、有机铋化合物、钛酸酯类化合物、α硅烷偶联剂、路易斯酸类、路易斯碱类化合物中的一种或几种。
9.根据权利要求1所述的紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料,其特征在于,所述阻聚剂为对苯二酚、对叔丁基邻苯二酚、2,6-二叔丁基对甲基苯酚、4,4'-二经基联苯、双酚A、对苯醌、吩噻嗪中的一种或几种。
10.一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料的制备方法,其特征在于,包括如下步骤:将多元醇类化合物烘干,烘干后溶于足量二甲苯中,加入二异氰酸酯,搅拌均匀后,加入催化剂,升温反应;再投入羟烷基封端的聚硅氧烷和羟基封端的聚醚,反应;最后向体系内投入阻聚剂,搅拌均匀后投入丙烯酸酯封端剂,反应;反应全程保持通入氮气并冷凝回流,反应结束以NCO特征峰消失为准;
将制得的保护涂料与光引发剂混合均匀后,涂布于PET或聚酰亚胺基材上,在空气氛围下进行紫外光照,紫外光波长310-460nm,固化时间5-35s,得到紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂层。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210281477.6A CN114621673A (zh) | 2022-03-22 | 2022-03-22 | 一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210281477.6A CN114621673A (zh) | 2022-03-22 | 2022-03-22 | 一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114621673A true CN114621673A (zh) | 2022-06-14 |
Family
ID=81904755
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210281477.6A Pending CN114621673A (zh) | 2022-03-22 | 2022-03-22 | 一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114621673A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN118185550A (zh) * | 2023-06-09 | 2024-06-14 | 东莞市百拓实业有限公司 | 一种用于偏光膜的高粘接力uv胶及其制备方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101481448A (zh) * | 2009-02-03 | 2009-07-15 | 广州慧谷化学有限公司 | 活性低聚物、其制备方法及含有该低聚物的耐白板笔擦写的紫外光固化涂料 |
CN103483537A (zh) * | 2013-09-26 | 2014-01-01 | 湖南本安亚大新材料有限公司 | 一种紫外光固化树脂、其制备方法以及用其所制备的涂料 |
CN103666241A (zh) * | 2013-12-05 | 2014-03-26 | 武汉绿凯科技有限公司 | 一种复合纳米水性uv涂料及其制备方法 |
CN104693409A (zh) * | 2015-03-30 | 2015-06-10 | 江门职业技术学院 | 柔性可调的加核型超支化聚氨酯丙烯酸酯树脂及制备方法 |
CN106675383A (zh) * | 2016-12-30 | 2017-05-17 | 江南大学 | 一种自修复型紫外光固化防涂鸦树脂及其制备方法 |
EP3461851A1 (de) * | 2017-09-27 | 2019-04-03 | Basf Se | Polyurethangiesselastomer |
CN111393608A (zh) * | 2019-08-21 | 2020-07-10 | 杭州师范大学 | 一种uv固化有机硅改性超支化聚氨酯材料的制备方法 |
CN113980240A (zh) * | 2021-11-08 | 2022-01-28 | 山东灵晓新材料有限公司 | 一种可uv光固化的超支化有机硅改性聚氨酯及涂层 |
CN114149565A (zh) * | 2021-11-30 | 2022-03-08 | 江苏三木化工股份有限公司 | 一种可光固化的超支化聚氨酯-环氧丙烯酸酯的制备方法 |
-
2022
- 2022-03-22 CN CN202210281477.6A patent/CN114621673A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101481448A (zh) * | 2009-02-03 | 2009-07-15 | 广州慧谷化学有限公司 | 活性低聚物、其制备方法及含有该低聚物的耐白板笔擦写的紫外光固化涂料 |
CN103483537A (zh) * | 2013-09-26 | 2014-01-01 | 湖南本安亚大新材料有限公司 | 一种紫外光固化树脂、其制备方法以及用其所制备的涂料 |
CN103666241A (zh) * | 2013-12-05 | 2014-03-26 | 武汉绿凯科技有限公司 | 一种复合纳米水性uv涂料及其制备方法 |
CN104693409A (zh) * | 2015-03-30 | 2015-06-10 | 江门职业技术学院 | 柔性可调的加核型超支化聚氨酯丙烯酸酯树脂及制备方法 |
CN106675383A (zh) * | 2016-12-30 | 2017-05-17 | 江南大学 | 一种自修复型紫外光固化防涂鸦树脂及其制备方法 |
EP3461851A1 (de) * | 2017-09-27 | 2019-04-03 | Basf Se | Polyurethangiesselastomer |
CN111393608A (zh) * | 2019-08-21 | 2020-07-10 | 杭州师范大学 | 一种uv固化有机硅改性超支化聚氨酯材料的制备方法 |
CN113980240A (zh) * | 2021-11-08 | 2022-01-28 | 山东灵晓新材料有限公司 | 一种可uv光固化的超支化有机硅改性聚氨酯及涂层 |
CN114149565A (zh) * | 2021-11-30 | 2022-03-08 | 江苏三木化工股份有限公司 | 一种可光固化的超支化聚氨酯-环氧丙烯酸酯的制备方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN118185550A (zh) * | 2023-06-09 | 2024-06-14 | 东莞市百拓实业有限公司 | 一种用于偏光膜的高粘接力uv胶及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7759405B2 (en) | Low viscosity multi-functional urethane acrylate oligomer-containing high solid UV curable coating composition | |
US10851195B2 (en) | Polyurethane (meth)acrylate oligomers and curable compositions comprising said oligomers | |
CN102702469B (zh) | 可紫外光固化的水性聚氨酯分散体及其制备方法 | |
CN108329342B (zh) | 一种有机硅偶联剂及其制备方法和应用 | |
TWI634168B (zh) | Film coating agent | |
CN111171702B (zh) | 双重固化的聚氨酯水分散体及水性uv涂料 | |
CN114621673A (zh) | 一种紫外光固化超支化聚硅氧烷/聚醚改性聚氨酯保护涂料及其制备方法 | |
EP2647678A1 (en) | Clear coating composition and method for forming multilayer coating film that uses same | |
Bhusari et al. | Effects of NCO: OH ratio and HEMA on the physicochemical properties of photocurable poly (ester-urethane) methacrylates | |
CN110498813B (zh) | 一种含氯含磷丙烯酸酯低聚物及其制备方法 | |
CN115466568B (zh) | 一种紫外光/湿气双重固化防护涂料及其制备方法和应用 | |
CN107722687B (zh) | 水性可剥离树脂及其制备方法 | |
CN107141440B (zh) | 一种刚性环改性的有机硅聚氨酯丙烯酸酯水性低聚物及其制备方法 | |
KR100205280B1 (ko) | 자외선 경화형 수용성 우레탄 아크릴레이트 화합물, 그의 제조방법 및 그의 수용화 방법 | |
CN112321842A (zh) | 一种紫外光固化超支化丙烯酸酯树脂及其制造方法 | |
KR100390478B1 (ko) | 우레탄 아크릴레이트 올리고머의 제조 방법 및 이를포함하는 자외선 경화형 도막 조성물 | |
KR101400120B1 (ko) | 광경화형 도료 조성물 | |
CN111377817A (zh) | 树脂与墨水 | |
CN117363199B (zh) | 一种可双重固化的聚氨酯涂料及其制备方法 | |
CN114591487B (zh) | 一种双组份uv固化水性聚氨酯乳液及其制备方法和应用 | |
US20200207907A1 (en) | Waterborne polyurethane and preparation method thereof | |
CN115536809B (zh) | 低光泽高物性自消光水性uv聚氨酯分散体及其制备方法 | |
TWI704204B (zh) | 水性聚氨酯及其製備方法 | |
JP2004035738A (ja) | 光硬化性樹脂組成物 | |
JP7382250B2 (ja) | ポリウレアポリウレア化合物とこれを含む組成物ならびにポリウレア硬化物、およびポリウレア硬化物を含む成形フィルムならびに成形品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220614 |
|
RJ01 | Rejection of invention patent application after publication |